THE SULPHURIC ACID SOLVENT SYSTEM: PART III. THE PREPARATION AND STRUCTURES OF SOME COMPLEX SULPHATOBORATES

1962 ◽  
Vol 40 (5) ◽  
pp. 1009-1017 ◽  
Author(s):  
R. J. Gillespie
Keyword(s):  
Boric Acid ◽  
Sulphuric Acid ◽  
Solvent System ◽  
Membered Ring ◽  
Acid Solutions ◽  
Sodium Potassium ◽  
System Part

By neutralizing sulphuric acid solutions of tetra(hydrogensulphato)boric acid with various metal hydrogensulphates, sodium, potassium, ammonium, and strontium salts have been prepared. From the compositions of these salts, and from the results of cryoscopic and conductimetric measurements on their solutions in sulphuric acid, it is concluded that they are best formulated as polysulphatoborates containing the six-membered ring [Formula: see text]It is shown that previously described sulphato compounds of boron can also be satisfactorily formulated on this basis.

THE RAMAN SPECTRUM OF THE SULPHURIC ACIDIUM ION: THE CONSTITUTION OF CONCENTRATED SOLUTIONS OF TETRA(HYDROGENSULPHATO)BORIC ACID IN SULPHURIC ACID

1962 ◽  
Vol 40 (4) ◽  
pp. 784-787 ◽  
Author(s):  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Raman Spectrum ◽  
Boric Acid ◽  
Sulphuric Acid ◽  
Raman Spectra ◽  
Acid Solutions ◽  
Concentrated Solutions

The Raman spectra of sulphuric acid solutions of tetra(hydrogensulphato)boric acid and its sodium and hydronium salts have been examined. Frequencies are assigned to some of the vibrations of the sulphuric acidium ion, H3SO4+, and are compared with the frequencies of the analogous vibrations of H2SO4 and HSO4−. Evidence is presented that elimination of disulphuric acid occurs between molecules of HB(HSO4)4 to give polymers containing B—O—B linkages.

THE SULPHURIC ACID SOLVENT SYSTEM: PART VI. THE BASICITIES OF COMPOUNDS CONTAINING SULPHUR–OXYGEN BONDS

1964 ◽  
Vol 42 (5) ◽  
pp. 1113-1122 ◽  
Author(s):  
S. K. Hall ◽  
E. A. Robinson
Keyword(s):  
Nitrogen Atom ◽  
Sulphuric Acid ◽  
Solvent System ◽  
Dimethyl Sulphoxide ◽  
Strong Base ◽  
Weak Bases ◽  
System Part ◽  
Sulphur Trioxide ◽  
Basic Behavior

Cryoscopic and conductimetric studies of a variety of compounds containing S—O bonds have shown that dimethyl sulphoxide behaves as a strong base in sulphuric acid whereas dialkyl sulphones behave as weak bases. In contrast diaryl sulphones and aryl sulphonic acids behave as non-electrolytes.A correlation is established between the basicities of the alkyl sulphones, H2SO4, and the HSO4− ion, and their sulphur–oxygen stretching frequencies. This relation is used to predict the basicities of other compounds containing S—O bonds. In particular it is shown that the basicity of monomeric sulphur trioxide is similar to that of sulphuric acid, and sulphamide is shown to behave as a strong base in sulphuric acid, which implies protonation on a nitrogen atom rather than on oxygen, since the S—O stretching frequencies indicate only weakly basic behavior for O-protonation.

The chlorosulfuric acid solvent system. Part II. The solutes SeCl4 and TeCl4; evidence for the formation of the SeCl3+ and TeCl3+ ions

1968 ◽  
Vol 46 (20) ◽  
pp. 3197-3200 ◽  
Author(s):  
E. A. Robinson ◽  
J. A. Ciruna
Keyword(s):  
Electrical Conductivity ◽  
Raman Spectra ◽  
Vibrational Spectra ◽  
Strong Acid ◽  
Ionic Species ◽  
Solvent System ◽  
Acid Solutions ◽  
Conductivity Measurements ◽  
System Part

From the results of electrical conductivity measurements on solutions in chlorosulfuric acid and the Raman spectra of solutions in chlorosulfuric acid (and fluorosulfuric acid) it is shown that SeCl4 and TeCl4 ionize quantitatively in these strong acid solutions to give the SeCl3+ and TeCl3+ cations.By comparison of the spectra with the vibrational spectra of solid SeCl4 and solid TeCl4, reported by other workers, it is suggested that the solids contain covalent MCl4 molecules rather than the ionic species MCl3+•Cl−, suggested previously.

THE SULPHURIC ACID SOLVENT SYSTEM: PART IV. SULPHATOCOMPOUNDS OF ARSENIC (III)

1963 ◽  
Vol 41 (2) ◽  
pp. 450-459 ◽  
Author(s):  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Sulphuric Acid ◽  
Solvent System ◽  
Dilute Solutions ◽  
Polymeric Compound ◽  
Polymeric Species ◽  
System Part ◽  
Hydrogen Sulphate ◽  
Sulphur Trioxide

The cryoscopic and conductimetric behavior of arsenic (III) oxide in 100% sulphuric acid and in dilute oleum have been investigated. It is concluded that in very dilute solutions in 100% sulphuric acid, arsenic (III) oxide forms arsonyl (III) hydrogen sulphate, AsO.HSO4, which is partly ionized to give the AsO+ cation. Both these species probably exist mainly in solvated forms, e.g., As(OH)(SO4H)2, and As(OH)(SO4H)+ respectively. At higher concentrations polymeric species such as HO.As(HSO4)OAs(HSO4)2 are present in increasing amounts and eventually the insoluble polymeric compound [(AsO)2SO4]n separates from solution. In oleum the more sulphated species As(HSO4)3, [(HSO4)2As]2O, and [(HSO4)2As]2SO4 are formed. Related structures are proposed for some previously prepared compounds of arsenic (III) oxide and sulphur trioxide.

THE SULPHURIC ACID SOLVENT SYSTEM: PART I. ACID-BASE REACTIONS

1960 ◽  
Vol 38 (8) ◽  
pp. 1363-1370 ◽  
Author(s):  
R. H. Flowers ◽  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Electrical Conductivity ◽  
Sulphuric Acid ◽  
Dissociation Constants ◽  
Solvent System ◽  
Conductivity Measurements ◽  
Acid Base ◽  
Acid And Base ◽  
System Part ◽  
Acids And Bases ◽  
Good Agreement

Acid–base reactions in the solvent sulphuric acid are discussed. Such reactions are conveniently studied by electrical conductivity measurements. A relation between the composition at which the conductivity has a minimum value and the strengths of the acid and base is derived. Values of the dissociation constants of acids and bases obtained in this way are shown to be in good agreement with values obtained by other methods.

THE SULPHURIC ACID SOLVENT SYSTEM: PART II. CONDUCTIVITY MEASUREMENTS ON SOLUTIONS OF SOME ACIDS

1961 ◽  
Vol 39 (6) ◽  
pp. 1266-1273 ◽  
Author(s):  
J. Barr ◽  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Dissociation Constant ◽  
Sulphuric Acid ◽  
Dissociation Constants ◽  
Solvent System ◽  
Acid Dissociation ◽  
Acid System ◽  
Conductivity Measurements ◽  
Acid Dissociation Constants ◽  
Strong Base ◽  
System Part

Conductivity measurements have been made on solutions of the following substances in sulphuric acid: HClO4, HSO3F, HSO3Cl, HPO2F2, HAs(HSO4)4, CH3SO3H, and CF3CO2H. Of these substances HSO3F, HSO3Cl, HAs(HSO4)4, and probably HClO4, behave as acids, CF3CO2H is a non-electrolyte, and HPO2F2, and probably CH3SO3H, are bases of the sulphuric acid system. Acid dissociation constants for HSO3F, HSO3Cl, and HAs(HSO4)4 have been determined by comparing the conductivities of their solutions with those of H2S2O7, whose dissociation constant is known from other measurements, and also by conductimetric titration with a strong base, e.g. KHSO4. These acids of the sulphuric acid system decrease in strength in the order HSO3F > HAs(HSO4)4 > HSO3Cl > HClO4.

THE SULPHURIC ACID SOLVENT SYSTEM: PART V. SOLUTIONS OF SOME ORGANOSILICON COMPOUNDS

1963 ◽  
Vol 41 (10) ◽  
pp. 2464-2471 ◽  
Author(s):  
R. H. Flowers ◽  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Coordination Number ◽  
Sulphuric Acid ◽  
Solvent System ◽  
Organosilicon Compounds ◽  
Initial Product ◽  
System Part ◽  
Bridging Groups

The cryoscopic and conductimetric behavior of solutions of hexamethyldisiloxane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, and tetraphenylsilane in 100% sulphuric acid has been investigated. The measurements show that stable non-electrolytes such as (CH3)3Si·HSO4 and (CH3)2Si(HSO4)2 are formed from the tri- and di-alkyl compounds. Species such as CH3Si(HSO4)3, which are presumably formed in the reaction of monoalkyl compounds, and Si(HSO4)4, which it is reasonable to suppose is the initial product from the cleavage of tetraphenylsilane, are unstable and polymerize to give polymers containing Si—O—Si bridging groups. No evidence was obtained for the formation of siliconium ions or for the formation of compounds containing silicon with a coordination number greater than four.

Standard Potentials in Aqueous Hydrochloric Acid Solutions Containing Boric Acid

1959 ◽  
Vol 22 (3_4) ◽  
pp. 179-186 ◽  
Author(s):  
Hussein Sadek ◽  
Th. F. Tadros
Keyword(s):  
Hydrochloric Acid ◽  
Boric Acid ◽  
Acid Solutions ◽  
Aqueous Hydrochloric Acid ◽  
Hydrochloric Acid Solutions

The role of surface crystalline heterogeneities in the electrooxidation of carbon monoxide adsorbed on Rh(111) electrodes in sulphuric acid solutions

1997 ◽  
Vol 432 (1-2) ◽  
pp. 1-5 ◽  
Author(s):  
Roberto Gómez ◽  
JoséM. Orts ◽  
Juan M. Feliu ◽  
Jean Clavilier ◽  
Lorena H. Klein
Keyword(s):  
Carbon Monoxide ◽  
Sulphuric Acid ◽  
Acid Solutions
Sign in / Sign up

Export Citation Format

Share Document